Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S526/909—Polymerization characterized by particle size of product
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S526/922—Polymerization process of ethylenic monomers using manipulative technique

Definitions

• the present invention relates to a process for the continuous preparation of a finely divided homopolymer of ethene or copolymer of ethene with a minor amount of C 3 -C 8 - ⁇ -monoolefin, with an average particle diameter (by DIN 53,477) of from 0.3 to 1.5, in particular of from 0.5 to 1.2, mm and a bulk density (by DIN 53,468) of from 0.400 to 0.600, in particular from 0.450 to 0.550, g/cm 3 by catalytic polymerization at from 60° to 100° C., in particular from 70° to 90° C., and under a total pressure of from 30 to 50, in particular from 35 to 45, bar in a circular tube reactor using a C 4 -C 8 -alkane, in particular a C 4 -C 6 -alkane, which is present in liquid form as reaction medium in which the ethene or ethene/comonomer mixture to be polymerized is present in dissolved form
• this object is achieved by (a) maintaining the mean concentration C m of polymer in the cycle stream at a value within a certain range and (b) effecting the bleeding out of reaction mixture at a point of the cycle stream where the concentration of polymer is lower than the mean concentration C m by a distinct and defined amount.
• the present invention accordingly provides a process for the continuous preparation of a finely divided homopolymer of ethene or copolymer of ethene with a minor amount of C 3 -C 8 - ⁇ -monoolefin, with an average particle diameter (by DIN 53,477) of from 0.3 to 1.5, in particular of from 0.5 to 1.2, mm and a bulk density (by DIN 53,468) of from 0.400 to 0.600, in particular from 0.450 to 0.550, g/cm 3 by catalytic polymerization at from 60° to 100° C., in particular from 70° to 90° C., and under a total pressure of from 30 to 50, in particular from 35 to 45, bar in a circular tube reactor using a C 4 -C 8 -alkane, in particular a C 4 -C 6 -alkane, which is present in liquid form as reaction medium in which the ethene or ethene/comonomer mixture to be polymerized is present in dissolved form and
• the process according to the invention comprises
• the process according to the invention additionally comprises effecting the catalytic polymerization by means of a Ziegler catalyst system composed of
• X is OR, chlorine, bromine or hydrogen, preferably OR or chlorine,
• R is C 1 -C 18 -hydrocarbyl, in particular C 1 -C 12 -alkyl and preferably C 2 -C 8 -alkyl, and
• n is a number from 1 to 3, preferably a number from 2 to 3, and
• the atomic ratio of transition metal of catalyst component (1):aluminum of catalyst component (2) ranges from 1:0.1 to 1:500, preferably from 1:0.2 to 1:50
• the molar ratio of organoaluminum catalyst component (2):organohalogen catalyst component (3) ranges from 1:0.001 to 1:20, preferably from 1:0.01 to 1:5, and subject to the special provision
• the transition metal catalyst component used is the solid phase product (VI) obtained by
• a finely divided porous inorganic oxidic substance (I) which possesses a particle diameter of from 1 to 1,000 ⁇ m, preferably from 1 to 400 ⁇ m, a pore volume of from 0.3 to 3 cm 3 /g, preferably from 1 to 2.5 cm 3 /g, and a surface area of from 100 to 1,000 m 2 /g, preferably from 200 to 400 m 2 /g, and has the formula SiO 2 . aAl 2 O 3 , where a is a number within the range from 0 to 2, in particular from 0 to 0.5, and
• (IIb1) 100 mole parts of a vanadium trihalide/alcohol complex of the formula VY 3 .nZ--OH, where Y is chlorine or bromine, preferably chlorine, n is a number from 1 to 6, preferably from 3 to 4, and Z is monovalent saturated aliphatic or partly saturated aliphatic, partly aromatic hydrocarbyl of not more than 10, preferably not more than 8, carbon atoms, in particular alkyl of not more than 6 carbon atoms,
• (IIb2) from 0.2 to 300, preferably from 0.5 to 100, mole parts of a titanium trihalide, where the halogen can be chlorine and/or bromine, preferably of titanium trichloride or of a titanium trihalide/alcohol complex of the formula TiY 3 .nZ--OH, where Y is chlorine or bromine, preferably chlorine, n is a number from 1 to 6, preferably from 3 to 4, and Z is monovalent saturated aliphatic or partly saturated aliphatic, partly aromatic hydrocarbyl of not more than 10, preferably not more than 8, carbon atoms, in particular alkyl of not more than 4 carbon atoms, and
• an aluminum compound (V) of the formula AlR m X 3-m where X is OR, chlorine, bromine or hydrogen, preferably OR or chlorine,
• R is C 1 -C 18 -hydrocarbyl, in particular C 1 -C 12 -alkyl, and preferably C 2 -C 8 -alkyl, and m is a number from 1 to 3, preferably 2, to form a suspension, with the proviso that the weight ratio of solid phase intermediate (IV): aluminum compound (V) ranges from 1:0.05 to 1:2, preferably from 1:0.1 to 1:1, the solid phase product (VI) which is the resulting suspended matter being the transition metal catalyst component (1).
• This novel process falls within the general category of processes for the continuous preparation of finely divided homopolymers of ethene or copolymers of ethene with minor amounts of ⁇ -monoolefins by catalytic polymerization in a liquid alkane as reaction medium containing the monomer or monomer mixture to be polymerized in dissolved form and the particulate polymer formed in suspended form under elevated temperature and pressure conditions by running the reaction mixture as a cycle stream to which the starting materials are added by bleeding in and from which the particulate product formed is withdrawn by bleeding out reaction mixture and wherein the catalytic polymerization is preferably effected by means of a specifically chosen Ziegler catalyst system.
• reaction medium used was isobutane.
• the reference standard for the absolute amounts of these catalyst components was the concentration of triisobutylaluminum in the reaction mixture, which was maintained at a constant 135 mg/kg of isobutane.
• reaction mixture was run as a cycle stream with a speed of 8 m/s.
• the starting materials used were 25 parts by weight of silicone dioxide (SiO 2 , particle diameter: 20-60 ⁇ m, pore volume: 1.75 cm 3 /g, surface area: 340 m 2 /g) and a solution of 100 parts by weight of tetrahydrofuran and 12.5 parts by weight of a transition metal composition composed of 100 mole parts of a vanadium trihalide/alcohol complex of the formula VCl 3 .4 ZOH, where Z is isopropyl, 1.3 mole parts of a titanium trihalide of the formula TiCl 3 .1/3 AlCl 3 and 6.7 mole parts of zirconium tetrachloride. These two components were combined, and the resulting suspension was briefly stirred. Thereafter the solid phase intermediate which had formed was isolated by driving off the volatile constituents in a rotary evaporator brought to an operating pressure of 10 mbar and an operating temperature of 70° C.
• silicone dioxide SiO 2 , particle diameter: 20-60 ⁇ m, pore volume:
• the sieves (testing sieves) are round; their sieve areas have a diameter of 200 mm.
• the sieve walls and the sieve netting consist of metal. Lids, all sieve drums and bottom plates, in a tightly closing way, fit on or into one another. They are strung with testing sieve netting according to DIN 4188. In most cases, a sieve set with testing sieve nettings according to Table 1 is sufficient.
• testing sieves with a netting with larger mesh widths may be added, in which case the geometrical series must be maintained.
• Cubes made of rubber of an edge length of 18 mm; hardness (70+3) shore of DIN 53505; apparent density 1.6 to 1.7 g/cm 3 .
• the corners and edges of the cube must be rounded in such a way that surfaces having a diameter of 15 mm are created as the sides of the cubes.
• a microchronometer with a division of the dial into minutes or less is used.
• a scale must be used that has a margin of error of ⁇ 0.1 g.
• the set of sieves is mounted on the sifting machine and is grounded so that electrostatic charges are avoided.
• the set of sieves is vibrated for 10 minutes ⁇ 15 seconds. After the vibrating, the individual sieves are carefully disconnected, and the quantities remaining on the sieves and on the bottom plate are weighed to 0.1 g. This takes place either by transferring the individual particle sizes (fractions--translator) to weighing receptacles (such as porcelain, plastic or metal bowls, weighing bottles, moisture-resistant paper pads or directly into the scales) that previously were also weighted to 0.1 g, or by weighing out the individual testing sieves and the bottom plate with the contents and subtracting the determined tare weights for the sieves and the bottom plate.
• the molding material particles adhering to the walls and nettings of the sieves, before the weighing, by means of a soft brush, must be added completely to the amount of the pertaining particle size (fraction--translator).
• Feeding funnel for example, of metal
• the feeding funnel has a capacity of approximately 200 ml; it is fastened at a stand at an indicated height. Its interior wall is polished.
• a 110 to 120 ml sample is loosely filled into the feeding funnel.
• the measuring cup is weighed in to 0.1 g (G 0 in g) and is placed vertically under the feeding funnel.
• the drop bottom of the feeding funnel is opened up so that the sample falls into the measuring cup. If required, the flowing of the sample can be aided by stirring with a rod.
• the apparent density is determined on three samples.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Processes Of Treating Macromolecular Substances (AREA)

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Cited By (19)

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Citations (8)

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• 1986
  • 1986-04-12 DE DE19863612376 patent/DE3612376A1/de not_active Withdrawn
• 1987
  • 1987-04-03 EP EP87104968A patent/EP0249698B1/fr not_active Expired - Lifetime
  • 1987-04-03 AT AT87104968T patent/ATE73141T1/de not_active IP Right Cessation
  • 1987-04-03 DE DE8787104968T patent/DE3776976D1/de not_active Expired - Lifetime
  • 1987-04-08 US US07/035,919 patent/US4794151A/en not_active Expired - Fee Related

Patent Citations (8)

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